Liquid developers containing azo dyes

ABSTRACT

A LIQUID DEVELOPER COMPRISING A DISPERSION OF A DYE OR PIGMENT HAVING A LONG CHAIN ALKYL GROUP IN THE MOLECULE STRUCTURE IN A LIQUID HYDROCARBON. THE LIQUID DEVELOPER FOR ELECTROPHOTOGRAPHY IS EXCELLENT IN DISPERSIBILITY OF THE IMAGE-FORMING DYE OR PIGMENT PARTICLES, UNIFORMITY IN CHARGE POLARITY, STORAGE STABILITY, DISTINCT-IMAGE FORMING ABILITY AND IMAGE-FIXING PROPERTY, AND SUCH LIQUID DEVELOPER CAN BE PREPARED WITHOUT AID OF CONVENTIONAL MODIFIERS SUCH AS CONTROL AGENTS, DISPERSING AGENTS AND FIXING AGENTS.

United States Patent Oflice 3,781,208 Patented Dec. 25, 1973 3 781 208 LIQUID DEVELOPERS CI JNTAINING AZO DYES Yasuo Ueda, Kobe, Yasutoki Kamezawa and Tatsuo Aiz awa, Osaka, and Toshimitu Ikeda, Himeji, Japan, gssrgnors to Mita Industrial Company Limited, Osaka,

apan No Drawing. Filed Apr. 28, 1970, Ser. No. 32,733

Int. Cl. G03g 9/04 U.S, Cl. 252-621 g 10 Claims ABSTRACT OF THE DISCLOSURE This invention relates to a liquid developer for electrophotography. More specifically, it relates to a liquid developer for electrophotography which consists essentially of a dispersion of coloring particles in an electrically insulating carrier liquid.

In electrophotography (inclusive of electrostatic printing), formation of visible images is accomplished by applying charged coloring particles onto an electrostatically charged pattern and converting an electrostatic latent image to an image of coloring particles.

Liquid developers prepared by'dispersing a coloring material in a highly dielectric liquid have been used for a longtime for formation of visible images from electrostatic latent images. For instance, the early liquid developing methods such as disclosed in the specifications of British Pat. No. 755,486 and French Pat. No. 1,112,- 180, include a technique of applying a dispersion of powder which will be electrically drawn, such as carbon black, in a high electric resistance liquid which is an organic liquid such as various hydrocarbons, e.g., carbon tetrachloride and ordinary insulating oil. Journal of Scientific Instruments, vol. 32, p. 74 (1955) and ibid, vol. 33, p. 194 (1965) discloses dispersions of pigments such as talc, magnesia, carbon black, Monolite Red RS, Monolite Yellow GNS, phthalocyanine blue, waxoline nigrosine, zinc oxide, Hansa Yellow, and Cadmium sulfide, in a liquid of a'high electric resistance such as turpentine oil, gasoline, kerosine, benzene and carbon tetrachloride, and teaches that linseed oil or synthetic resin is further added to these dispersions for controlling charges on coloring particles and fixing visible images.

The specification of Japanese Pat. No. 273,198 (patent publication No. 13,424/60) discloses a dispersion of a pigment in a liquid of a high electric resistance and teaches that the pigment is made electrically selective to charges of latent images by coating the pigment with a control agent such as an alkyd resin, linseed oil, synthetic polystyrene rubber or wax rubber.

After the issuance of the above Japanese patent, various studies have been reported and research made with a view to attaining effective control of charge polarity of coloring particles and improvements in stability of dispersions and fixing propery of visible images, and methods have been proposed using various synthetic and natural resins, synthetic resin monomers, primary condensates thereof, surface active agents and the like as the substance to coat coloring particles or to be dissolved in a carrier liquid of a high electric resistance.

The important problems generally involved in liquid developers reside firstly in the uniformity and dispersion stability of charged particles dispersed in the carrier liquid and secondarily in the distinction and fast fixing of images formed by development.

However, these conventional liquid developers are fatally defective with respect to uniformity in charge polarity of dispersed particles, image-fixing property, duration of activity and stability under long time storage.

More specifically, in the case of liquid developers prepared by dispersing dyes or pigments directly in an electrically insulating liquid, resulting visible images of coloring material particles are poor in fixing property and additional operations are necessary for fixing these visible images. Further, since the electrical charges of the dispersed particles of dyes or pigments is not uniform, it is frequently difficult to obtain distinct images.

In the case of liquid developers prepared by using additives such as dispersing assistants in addition to dyes or pigments, an excellent dispersion condition is attained just after dispersing the coloring materials and distinct images can be developed with such liquid developers just after their preparation. However, the balance between the carrier liquid and the coloring material as well as the above-mentioned additives is lost with the lapse of time under continuous usage or storage, resulting in aggregation of coloring material particles, deterioration in electrical properties such as uniformity in charge polarity, precipitation of particles and increasing obscurity in the finished images. Thus, the developers become unsuitable for practical use.

Generally speaking, additives which are excellent as agents for dispersing the coloring material gradually deteriorate the electrical insulating property of the carrier liquid and cause coloring material particles to gradually lose their electrical charges. Further, additives capable of promoting the fixing of coloring material particles often precipitate as the result of oxidation, polymerizatino, gelation and the like. Still further, control agents used to coat pigment particles not only gradually lose the controlling activity when dissolved in the carrier liquid or separated from the particles, but also induce aggregation and precipitation of particles, making resulting images very indistinct.

Thus, although known liquid developers may possess excellent dispersibility and distinct-image forming ability just after their preparation, from the industrial viewpoint they are fatally defective in that they lack storage stability and they lose reproducibility of images with the lapse of time.

It has now been discovered that, quite independently of the conventional techniques of adding various modifiers such as control agents, dispersing agents, fixing agents and the like to the carrier liquid together with coloring material particles, when specific dyes which will be detailed hereinbelow are dispersed in an electrically insulating liquid, liquid developers for electrophotographycan be obtained which are excellent in dispersibility of imageforming particles, uniformity in charge polarity, storage of a dispersion of an anthraquinone dye or pigment, azo

dye or pigment, or phthalocyanine pigment substituted by (a) an alkyl group,

(b) an alkoxy group,

(c) a thioalkoxy group,

(d) an alkyl amino group,

(e) an alkylcarbonyl group,

(f) an N-alkylcarbonamide group,

(g) an N-alkylsulfonamide group,

(h) an alkarylamino group,

(i) an N-alkarylcarbonamide group,

(i) an N-alkarylsulfonamide group,

(k) an alkylbenzenesulfonamide group, (1) an alkoxyarylamino group, or

(m) an alkylamino-triazinylamino group,

each of the above groups (a) to (m) having 8 to 24 carbon atoms in the alkyl portion, in a liquid hydrocarbon.

According to this invention, anthraquinone dyes or pigments, azo dyes or pigments, or phthalocyanine pigments substituted by the above-mentioned substitutents having a long chain alkyl portion of 8 to 24 carbon atoms are dispersed in electrically insulating hydrocarbon liquids. When dyes having a specific combination of the above-mentioned substituent and dyestufi skeleton are dispersed in a hydrocarbon liquid, dispersions of these dyes finely and uniformly dispersed in the liquid are obtained, and these dispersions can retain their very stable dispersion state for a long period of time. More specifically, since the dyes or pigments dispersed in the hydrocarbon liquid have in their molecular structure a long chain alkyl group which is an oleophilic group, they can be finely dispersed in the electrically insulating hydrocarbon liquid by their own capacity and the resulting dispersion state is very stable. Although the state of charges of dispersed particles is influenced by the interfacial properties of the dispersed particles and the dispersion medium, in the liquid developer of this invention the dispersion state of the dye or pigment particles is uniform and therefore, the state of charges is also uniform.

Further, the dyes or pigments to be used as coloring material in this invention are prominently excellent in their property of fixing images of originals to be reproduced by electrophotography because of the above-mentioned specific combination of the specific substituent and the specific dyestufi skeleton.

It is quite unexpected that the above-mentioned excellent properties of the liquid developer of this invention can be attained without using any of the conventional control agents, dispersing agents or fixing agents.

In this invention, anthraquinone dyes or pigments having the above-mentioned substituents are conveniently used. These anthraquinone dyes or pigments are prominently excellent in their dispersibility and fixing property. These anthraquinone dyes or pigments may be the following Formula I:

Ra Br El Y R (h) an alkarylamino group,

(i) an N-alkarylcarbonamide group,

(j) an N-alkarylsulfonamide group,

(k) an alkylbenzenesulfonamide group, (1) an alkoxyarylamino group, and

(In) an alkylamino-triazinylamino group,

each of the above groups (a) to (111) having 8 to 24 carbon atoms, and wherein 1 to 4 of R to R are substituents selected from the groups (6) As such anthraquinone dyes or pigments of Formula I the following commercially available dyes in addition to those described specifically in examples given hereinbelow may be cited:

Carbolan Blue, product of Imperial Chemical Industries, Co.

SOaNa Carbolan Violet 2 R, product of Imperical Chemical Industries, Co.

In this invention azo dyes or pigments having the abovementioned substituents (a) to (m) may be used. These dyes or pigments can be expressed by the following Formula II or III:

wherein A and A each stand for a benzene, naphthalene or pyrazolone ring which may be substituted by a halogen atom, a hydroxy group, an amino group, a nitro group, a group $0 M (in which M is hydrogen, an alkali metal or an alkaline earth metal), an alkyl or alkoxy group having 1 to 4 carbon atoms or a phenyl group which may be substituted by a halogen atom, a hydroxyl group, an amino group, a nitro group or a group $0 M (in which M is as defined above); R and R each stand for (a) an alkyl group,

(b) an alkoxy group,

(0) a thioalkoxy group,

(d) an alkylamino group,

(e) an alkylcarbonyl group,

(f) an N-alkylcarbonamide group, (g) an N-alkylsulfonamide group, (h) an alkarylamino group,

(i) an 'N-alkarylcarbonamide group, (j) an N-alkarylsulfonamide group,

1 (R) an alklbenzenesulfonamide group,

(1) an alkoxyarllamino group, or (m) an alkylamino-triaainylamino group,

each of the above groups. (a) to (m) having 8 to 24 carbon atoms in the alkyl portion; n is 0 or 1; and Y is an arylene group which may be substituted by an alkyl or alkoxy group of 1 to 4 carbon atoms.

' As suitable azo dyes or pigments the following commercially available ones in addition to those described specifically in examples given herein below maybe cited:

(C.I. Direct Red 28-C H red) O H CH3 0 O OaNB S O Na (C.I. Direct Blue 8C H blue) S 0 aNa CH3 0 CH3 0 S O aNa.

NHz H (C.I. Direct Blue 22C H blue) mHn OH OaNB NaOaS S (red) eral formula:

R R N f mi? wherein M stands for a divalent metal such as copper and R is a substituent of the group consisting of (a) an alkyl group,

(b) an alkylcarbonyl group,

(c) an N-alkylsulfonamide group, and (d) an N-alkarylsulfonamide group,

each of the above groups (a) to (d) having 8 to 24 carbon atoms in the alkyl portion.

Dyes and pigments that are used particularly conveniently in this invention are those having an alkyl group CH3 0 H CiaHa 1s a of 8 to 24 carbon atoms bonded directly to a benzene or naphthalene ring. These dyes and pigments have excellent dispersibility in electrically insulating hydrocarbon liquids,

and they are also have an excellent self-fixing property to electrophotographic recording paper.

Particularly preferred anthraquinone dyes and pigments, are those expressed in above-mentioned General Formula I wherein 1 to 4 of R to R are substituents selected from alkarylarnino, N-alkarylcarbon, N-alkarylsulfonamide and alkylbenzenesulfonamide groups, each of which has 8 to 24 carbon atoms in the alkyl portion.

Particularly preferred azo dyes and pigments, are those expressed by above-mentioned General Formula H or III wherein R and R are selected from the group consisting of alkyl, alkarylamino, N-alkarylcarbonamide, N-alkarylsulfonamide and alkylbenzenesulfonamide groups, each of which has 8 to 24 carbon atomstin the alkyl portion.

-It is preferable that the alkaryl group in the abovementioned substituents is an alkylphenyl group expressed by the formula wherein n is an integer of from 8 to 24, such as p-decylphenyl, p-dodecylphenyl and p-octadecyl groups.

In the above anthraquinone dyes of Formula I and azo dyes of Formulae II and III, forms of acidic dyes having a sulfonic acid group or a sulfonic acid salt group may be converted to lakes of salts with barium or calcium. The use of such lakes can give a distinct visible image of a high concentration when they are combined with a suitable carrier liquid.

According to this invention, the above-mentioned specific dyes of pigments are dispersed in a liquid hydrocarbon to form liquid developers. In this invention it is unnecessary to use conventional modifying agents such as control agents, dispersing agents and fixing agents, and without the aid of such agents a liquid developer excellent in dispersibility of coloring particles and uniformity of electric charges can be obtained. The liquid developer of this invention can develop an electrostatic latent image to a distinct visible image of good fixing property.

tion are straight-chain aliphatic hydrocarbons such as n-hexane and n-octane; aliphatic hydrocarbon mixtures such as naphtha and kerosene; isoparafiin hydrocarbons having a boiling point of 80 to 210 C.; and liquid naphthene hydrocarbons such as cyclohexane.

It has now been found that when an aliphatic hydrocarbon containing 5 to 30% by volume, especially 10 to 30% by volume, of an aromatic liquid hydrocarbon is used as the liquid hydrocarbon in this invention, in development of an electrostatic latent image a visible image can be obtained with excellent image distinctiveness and fixing property. As the aromatic hydrocarbon benzene, toluene and xylene may be named, and the above recited aliphatic hydrocarbons may be used in this embodiment.

The concentration (consistency) of the dye or pigment in the liquid developer may be one usually adopted in the art. For instance, the dye or pigment is dispersed in the liquid hydrocarbon in such an amount that the resulting liquid developer contains 0.05 to 5 grams of the dye or pigment per liter of developer.

The dye or pigment may be finely dispersed in the liquid hydrocarbon medium. by dispersing the dye or pigment into a small amount of the medium under ultrasonic vibration or higher shear agitation and diluting the resulting batch with a great amount of the medium liquid.

The liquid developer of this invention can be used as the developer in various electrophotostatic methods. For instance, the liquid developer of this invention can be used for development according to an electrophotographic method using an electrophotographic recording paper comprising a photoconductive layer composed of a photoconductive material and a binder. Suitable recording papers are described in specifications of U.S. Pat. No. 3,052,539 and British Pat. No. 1,020,506. Furthermore, the liquid developer of this invention may also be applied with good results to development according to an electrophotographic method disclosed in, for instance, the specification of U.S. Pat. No. 2,833,648, in which an electrostatic latent image is transferred to an electrically insulating aper.

EXAMPLE 1 Synthesis: A reactor was charged with 1.4 g. of 1,5-dichloroanthraquinone, 33.6 g. of stearyl amine, 1.3 g. of sodium acetate, 0.3 g. of copper acetate and 3.2 g. of pyridine and the reaction was effected at 80 C. for 15 hours under stirring. The resulting red solid was dissolved in benzene and insoluble matters were removed, followed by distillation of benzene and recrystallization from glacial acetic acid. Thus 1,S-di-n-octadecylaminoanthraquinone was obtained by the reaction of the following formula:

ITIH C 181137 Preparation of liquid developer: A liquid developer was prepared by dispersing 0.2 g. of 1,5-di-n-octadecylamino- EXAMPLE 2 Synthesis: A reactor Was charged with 19 g. of l-amino- 2,4-dibromoanthraquinone, 28 g. of dodecylamine, 0.4 g. of copper acetate, 5 g. of potassium acetate and 40 g. of

' pyridine and the reaction was effected at an elevated temperature of 115-120" C. for 20 hours under stirring. The

reaction product was dissolved in benzene and insoluble matters were separated, followed by distillation of benzene and recrystallization from glacial acetic acid. A blue solid of 1 amino-2,4-di-n-dodecylaminoanthraquinone was obtained by the reaction of the following formula:

Preparation of liquid developer: A liquid developer was prepared by dispersing 0.2 g. of 1-amino-2,4-di-n-dodecylaminoanthraquinone in a mixed solvent of 100 ml. of xylene and 900 ml. of Isoper H (product of Esso Standard Petroleum Co.), which is an isoparatfin hydrocarbon, by conducting ultrasonic vibration for 5 minutes. The so formed liquid developer was adsorbed onto a negative electrostatic latent image, producing a blue visible image (positive) of good fixing property.

EXAMPLE 3 NHz + 2HBr (I? NH HBr Y Preparation of liquid developer: A liquid developer was prepared by dispersing 0.2 g. of the so formed blue solid in 1 liter of Isopar H (product of Escso Standard Petroleum Co.), which is an isoparafiin hydrocarbon, by means of ultrasonic vibration. The particles in the developer were negatively charged and reversed on a negative electrostatic latent image, forming a blue visible image (negative).

EXAMPLE 4 Synthesis: A reactor was charged with 9.5 g. of 1- amino-2,4-dibromo-anthraquinone, 1.5 g. of octadecyloxyaniline, 2.5 g. of potassium acetate, 0.2 g. of copper acetate and 20 g. of pyridine, and the reaction was eifected at an elevated temperature of 120 C. for 24 hours. The reaction mixture was cooled and filtered, after which the recovered precipitate was washed with pyridine, alcohol and then with water, and dried to yield l-amino-Z- bromo 4 -p-octadecyloxyanilinoanthraquinone.The reaction is expressed by thefDllOWiIlg formula:

O llIH-Q-O-Cmllu Preparation of liquid developer: A liquid developer was prepared by dispersing 0.2 g. of 1-amino-2-bromo-4-poctadecyloxyanilinoanthraquinone in 1 liter of Shellsol 71,

+ HBr (product of Shell Petroleum Co.), which is an isoparafiin hydrocarbon, by means of ultrasonic vibration. Particles in the so formed liquid developer were negatively charged and reversed on a negative electrostatic latent image to form a blue visible image (negative).

EXAMPLE blue precipitate was recovered by filtration, washed sufliciently and dried to yield 1-amino-2-p-n-hexadecylphenoxy 4-dodecylanilinoanthraquinone. The reaction is expressed by the following formula:

AEjOQaH. \E/ NEG-012E Preparation of liquid developer: A liquid developer was prepared by dispersing 0.2 g. of 1-amino-2-p-n-hexadecylphenoxy-4-p-dodecylanilinoanthraquinone in a mixed solvent of 100 ml. of toluene and 900 ml. of Isopar G (prod- ..uct of Esso Standard Petroleum Co.), which is an iso- ,of a saturated aqueous solution of sodium chloride containing ice, followed by filtration. The precipitate was washed with an aqueous solution of sodium chloride containing ice at a temperature lower than 5 C. to yield phthalocyanine tetrasulfochloride. Then, 1 g. of the so formed phthalocyanine tetrasulfochloride was added to '4. g. of octadecylamine molten at 70 C., followed by addition of several drops of pyridine. The reaction was effected for about 1.5 hours under stirring. The reaction mixture was poured into warm water and benzene was added thereto to extract the intended product in benzene. Benzene was removed from the extract by evaporation. The resulting product was purified with glacial acetic acid to yield a blue solid of copper phthalocyanine tetra-N- octadecylsulfonamide.

The reaction of forming the above product is expressed by the following formula:

SOzCl DnNH:

SOzNHCmHu Preparation of liquid developer: Two liquid developers were prepared by dispersing 0.5 g. of the so formed blue solid of copper phthalocyanine tetra-N-octadecylsulfonamide in a mixed solvent of 150 ml. of Solbesso (product of Esso Standard Petroleum Co.), which is an aromatic hydrocarbon and 850 ml. of Isopar H (product of Esso Standard Petroleum Co.), which is an isoparaflin hydrocarbon, or in 1 liter of Whitesol (product of Kyodo Petroleum Co.), which is a petroleum hydrocarbon solvent of an aromatic content of 16%, respectively, by means of ultrasonic vibration. Each of the so prepared liquid developers was reversed on a negative electrostatic latent image, forming a beautiful blue visible image (negative) of good fixing property.

EXAMPLE 7 Example 6 was repeated by employing hexadecylamine instead of octadecylamine. A liquid developer similar to that obtained in Example 6 was obtained.

EXAMPLE 8 When Example 6 was repeated by using 1,2-hydroxyanthraquinone-3-sulfochloride instead of copper phthalo- 11 cyanine, 1,2-hydroxyanthraquinone 3 octadecylsulfonamide was obtained by the following reaction:

OH 0 OH ll l l OH +C a( 2)i1NH2 SOzCl A liquid developer prepared from the above product was reversed on a negative electrostatic image, producing a distinct reddish purple visible image (negative).

EXAMPLE 9 A mixture of 4 g. of chrysoidine and 20 g. of chlorosulfonic acid was stirred at a temperature lower than 20 C. for 2 hours and poured in ice water to salt out chrysoidine sulfochloride. Then 5 g. of chrysoidine sulfochloride were reacted with 20 g. of stearyl amine molten at 70 C. The reaction product was extracted with benzene and benzene was evaporated to yield the intended chrysoidine-N-stearylsulfonamide. A liquid developer was prepared by dispersing 0.1 g. of the resulting product in 1 liter of Shellsol 71 (product of Shell Petroleum Co.), which is an isoprafiin hydrocarbon, by effecting ultrasonic vibration for 2 minutes. This liquid developer was excellent in dispersibility and gave a yellow visible negative image of good fixing property.

For comparison, a liquid developer was prepared in the same manner as above by using 0.1 g. of chrysoidine powder. This comparative developer was very inferior in dispersibility and fixing property and gave an indistinct yellowish brown image.

The above reaction of forming chrysoidine-N-stearylsulfonamide is expressed by the following formula:

ITIHI @N=N-@NH2 OHa(CHz)11NH,

N=N- NH, H01

s OzNHC H 5 O NHC H31 EXAMPLE Synthesis: A reactor was charged with 3.4 g. 2-dodecylamino-4-, -dichloro-S-triazine, 2.6 g. of celliton blue and 12 Preparation of liquid developer: A blue-liquid developer was prepared by dispersing 0.1 g. ofythezso formed EXAMPLE 11 Synthesis: A reactor was charged with a solution of 9.2 g. of 2,4,6-trichloro-S-triazine in acetone, and a solution of 13.5 g. of octadecylamine in acetone was added thereto while the temperature was being maintained at 0-5 .C. by cooling the reactor with ice from the outside. Then, an aqueous solution of sodium carbonate was gradually added and the reaction was efiected at 05 C. for 3 hours. The reaction mixture was allowed to stand overnight, and was poured into water. The resulting-precipitate was recovered by filtration. 4.2 got the so obtained 2- octadecylamino-4,6-dichloro-S-triazine and 2.7 g. of celliton blue were dissolved in o-dichlorobenzene,.and the reaction was effected at 150 C. for 4 hours under stirring. The reaction mixture was cooled and poured into petroleum ether, followed by filtration and washing with acetone to yield a blue powder. 3.2 g. of the resulting blue powder were dissolved in ml. of dioxane, and 0.4g. of monoethanolamine was added thereto. The reaction was efiected at the boiling point under stirring. The reaction mixture was added to water, and the precipitate was recovered by filtration, washed with benzene and dissolved in acetone by heating. Insoluble matters were separated and then the liquid was cooled. Theresulting precipitated blue particles were covered by filtration and dried.

The above reaction of forming blue particles is expressed by the following formula:

N N (ll-f For Cl-f NHCmHu L] n u n N N N l NHCmHzh HzNCzHrOH Preparation of liquid developer: A blue liquid developer of an excellent dispersibility was prepared by dis- I persing'0.2 g. of the so formed b'lue'particles in a mixed solvent of 200 ml. of-benzene andof Isopar H (product of Esso Standard Petroleum C0., which is an isoparaffin hydrocarbon, by means of ultrasonic vibration. This liquid developer was reversed on a negative-electrostatic latent image, producing a blue visible negative image of good fixing property. f

EXAMPLE 12 recovered by filt'ration and washed'with acetone to yield a blue sub stance. A reactor was charged with 2 g. of the so formed blue substance, 26 g. of stearyl-amine and 100 ml of o-dichlorobenz'ene, and 'the reaction was effected at a temperature of 140 C. for 4'hours to obtain a faintly blue substance. f k

The reaction of forming theabove blue product is expressed by the following formula:

Preparation of liquid developer. A liquid developer was prepared by dispersing 0.2 g. of the so formed blue substance in a mixed solvent orzoo ml. of toluene and 800 ml. of Isoper G (product of Esso Standard Petroleum C0., which is an isoparaflin 'hydrocarbon,,by means of ultrasonic vibration. This liquid developer was very excellent in dispersibility, and particles of the developerwere adsorbed onto'a negative electrostatic latent image, forming a beautiful blue visible image (positive).

EXAMPLE 13 Synthesis: A reactor was charged with 30 g. of stearyl chloride, 15 g. of anhydrous aluminum chloride and 100 g. of dried carbon tetrachloride, and 5 g. of phthalocyanine blue were added thereto at an elevated temperature of -35 C, under stirring. The reaction was effected at this temperature for .4 hours u-nder stirring. The reaction mixture wasxpoured in water to decompose aluminum chloride. Then the mixture was washed several times with water and poured into acetone. The resulting precipitate was recovered by filtration, washed with warm ethanol and dried to obtain a blue product of tetra-octadecanoylphthalocyanine.

1.4- The reaction of forming the above blue product is expressed by the following formula:

Har n 0 Preparation of liquid developer: A liquid developer was prepared by dispersing 0.2 g. of the blue product in a mixture of 300 ml. of xylene and 700 ml. of Isopar G (product of'Esso Standard Petroleum Co.), which is an isoparaffin hydrocarbon solvent by elfecting ultrasonic vibration for 5 minutes. The liquid developer has superior particle dispersibility, image distinctiveness and image fixing property than the liquid developer prepared without addition of xylene, which is an aromatic solvent. Particles in the above developer were adsorbed onto a negative electrostatic latent image, forming a beautiful blue visible image (positive).

EXAMPLE 14 Synthesis: 41 g. of metanilic octadecanoylamide prepared by reducing the reaction product of l-nitrob'enzen'e- 3-sulfonamide and stearylchloride was dissolved in glacial acetic acid and diazotized with 25 g. of 30% hydrochloric acid and 7 g. of nitrous acid. The diazotized liquid was added to a liquid containing 1-(2',5'-dichloro-4-sulfonium)-3-methyl-5-pyrazolone and a suitable amount of caustic soda. The precipitating dye was recovered by filtration, washed and dried to yield the intended product.

The reaction of forming the above product is expressed by the following formula:

-S O NH 01711350 0 Cl reduction S Q NH C O 17115 diazotizlng N #1101 on S OzNHC O C 7H 5 S Call N oH somncoc uu Preparation of liquid developer: A liquid developer was prepared by dispersing 0.2 g. of the product in 1 liter of Whitesol (product of Kyodo Petroleum Co.), which is a petroleum hydrocarbon solvent of an aromatic content of 16%, by means of ultrasonic vibration. The particles of the liquid developer were adsorbed onto a negative electrostatic latent image, producing a beatutiful yellow visible image (positive).

EXAMPLE 15 Synthesis: 34.3 g. of octadecylaniline, 250 g. of 36% hydrochloric acid and 300 g. of water were mixed together at 50 C. After the mixture was cooled to 5 C., the diazotization was effected with nitrous acid, followed by coupling with H acid to obtain an intended blue dye.

The reaction of forming the blue dye is expressed by the following formula:

diazotizing OH NH:

man-Q-wm. Hots -sonar Synthesis: To a solution of 100 g. of 1,4-diamino-2- mercaptoanthraquinone in 1000 g. of alcohol 120 g. of hexadecyl were added. In a reactor equipped with a refluxing cooling tube, the reaction was effected at the boiling point under stirring for 2 hours. The reaction mixture was cooled, and the precipitate was recovered by filtration, washed with alcohol and'dried to obtain a waxy product. 1 r t The reaction of forming the above waxy product is expressed by the following formula:

Preparation of liquid developer: A liquid developer was prepared by dispersing 0.2 g. of the so formed waxy product in New Sol Delux (product of Nippon Nippon Petroleum 00.), which is a petroleum hydrocarbon solvent of an aromatic content of 8.2%, by means of ultrasonic vibration. Particles dispersed in the liquid developer were adsorbed onto a negative electrostatic latent image, producing a violet visible image (positive).

EXAMPLE 18 Synthesis: 10 g. of stearyl chloride and 7 g. of anhydrous aluminum chloride were dissolved in 50 g. of dried carbon tetrachloride, and 5 g. of Acid Fast Black BR (C.I. Acid Black 31; 17580) wereaddedto the solution under stirring while maintaining the temperature of the solution at 10-15" C. The reaction was effected at this temperature under stirring for 3 hours. The reaction product was poured into ice water and'neutralized with potassium hydroxide, followed by, removal of carbon tetrachloride by steam. distillation, washing with aqueous potassium hydroxide and drying toform octadecanoyl Acid Fast Black BR. Separately, 10 g. of ,zinc powder were added to a solution of 1 g. of mercuric chloride in 20 ml. of water and the mixture was shaken for- 1.5 hours. The supernatant liquid was removed by decantation and the residue was washed'sufiiciently with water to obtain amalgamated zinc. A'three-neck equipped with a refluxing cooling tube and a stirrer wascharged with 7 g. of the so formed amalgamated zinc, and then -10 ml. of water and 7 ml. of concentrated sulfuric acid were added there to. Finally, a solution of 5g. of octadecanoyl Acid Fast Black BR dispersed in 10 ml. of alcohol was added to the flask. The reaction was effected for 10 hours under vigorous agitation at the boiling point of the system. Octadecyl Acid Fast Black BR was obtained.

The above reaction of forming Octadecyl Acid Fast Black BR is expressed by the following formula:

( 2)11CHs I HO Preparation of liquid developer: A liquid developer was prepared by dispersing 0.2 g. of the so formed dye in 1 liter of Whitesol (product of Kyodo Petroleum Co.,), which is a petroleum hydrocarbon solvent of an aromatic content of 16%, by means of ultrasonic vibration. Particles of the liquid developer were adsorbed on a negative electrostatic latent image, forming a black visible image (positive). The liquid developer was excellent in dispersibility and image-fixing property.

EXAMPLE 19 A liquid developer prepared by adding 0.2 g. of Carbolan Crimson BS (acidic azo dye, product of Imperial Chemical Industries, Ltd., C.I. 18073) of the formula 7 H0 NHC OCH; a (CH2) nGN=N to 1 liter of Isopar G (product of Esso Standard Petroleum Co.), which is an isoparaffin hydrocarbon and subjecting the mixture to ultrasonic vibration for 5 minutes was compared with a liquid developer prepared by adding 0.2 g. of the same dye to a mixed solvent of 200 ml. of toluene and 800 ml. of Isopar G and subjecting the mixture to ultrasonic vibration for 5 minutes. The latter liquid developer was superior to the former with respect to image-distinctiveness, image-fixing property and particle dispersibility. Particles of the latter liquid developer were adsorbed on a negative electrostatic latent image, producing a beautiful red visible positive image of high -SO NB resolubility.

EXAMPLE 20 0.2 g. of a barium lake pigment of the formula H0 NHCOCH;

7 cust m) 11ON=N 133/ 038 SOgBa/2 prepared from Carbolan Crimson BS used in Example 19 was added to 200 ml. of benzene and dispersed therein by effecting ultrasonic vibration for 5 minutes. The resulting concentrated liquor was diluted with 800 ml. of Isopar H (product of Esso Standard Petroleum Co.), which is an'isoparaflin hydrocarbon, to form a dispersion. Particlesof the lake pigment were adsorbed on an electrostatic latent image, producing a red visible positive image of high resolubility and good water resistance with little edge effect. EXAMPLE 21 0.2 g. of Carbolan Yellow 3 GS of the formula I CH3 l8 (yellow; acidic azo dye, product of Imperial Chemical Industries Ltd., CI. 18961) was added to 1 liter of Shellsol 71 (product of Shell Petroleum Co.), which is an isoparaflin hydrocarbon, and the mixture was subjected to ultrasonic vibration for 5 minutes to form a liquid developer consisting of a dispersion of the dye into the hydrocarbon medium. Separately, another liquid developer was prepared by adding the same dye to a mixed solvent of 150 ml. of Solvesso 100 (product of Esso Standard Petroleum Co., aromatic solvent) and 850 ml. of Shellsol 71 and dispersing the dye in the mixed solvent by conducting ultrasonic vibration for 5 minutes. When both liquid developers were compared, it was found that the latter was superior to the former in image distinctiveness, fixing property and particle dispersibility.

Dye particles of the latter liquid developer were adsorbed on a negatively charged electrostatic latent image, forming a beautiful yellow positive visible image of high resolubility.

EXAMPLE 22 Synthesis: 10 g. of a reaction product of l-amino-Z- bromo-4-p-dodecylanilino-anthraquinone and p-n-hexadecyl phenol were charged with 10 g. of 100% sulfuric acid into a three neck flask equipped with a thermometer and a stirrer. The reaction was effected at C., and when the reaction mixture was soluble in water, a small amount of fuming sulfuric acid was added thereto, following which the system was added to water, salted out and filtered. The filtered matter was dissolved again in hot water, and an aqueous solution of barium chloride was added thereto at 50 C. under agitation, and the reaction was performed for 1 hour. The resulting precipitated was separated by filtration and dried to yield a product of the following formula O 17TH:

Preparation of liquid developer: A liquid developer was prepared by dispersing 0.2 g. of the above synthesized product into a mixed solvent of 200 ml. of toluene and 800 ml. of Shellsol 71 (isoparaffin hydrocarbon, product of Shell Petroleum Co.) by means of ultrasonic vibration. From this liquid developer a print of a blue visible image of clear contrast was obtained.

EXAMPLE 23 into water and dissolved therein by heating. Insoluble.

matters were separated by filtration, and the blue filtrate was admixed with an aqueous solution of calcium chloride to lake the dye. The precipitating lake was recovered by filtration, washed with water and dried to yield a blue solid.

The above reaction is expressed by the formula:

following EXAMPLE 24 Synthesis: 20 g. of 1,5-dichloroanthraquinone were added to 30 g. of fuming sulfuric acid (80;, content=40%), followed by agitation for 1 hour. Then, g. of fuming sulfuric acid (S0 content=60%) were added to the mixture within a period of time of 10 minutes and agitation was effected at 120 C. for 4 hours. Thereafter, the temperature of the mixture was lowered below 10 C. and it was poured into 200 cc. of water and 100 g. of ice, followed by removal of the unreacted anthraquinone by filtration. To the remaining transparent liquor 7 g. of potassium chloride were added to perform the salting out, followed by filtration and water- Washing to yield a potassium salt of 1,5-dichloroanthraquinone-4,8-disu1fonic acid.

2 g. of the so obtained potassium salt of 1,5-dichloroanthraquinone-4,8-disulfonic acid were charged together with 33 g. of stearyl-amine, 1.3 g. of sodium acetate, 0.3 g. of copper acetate and 3.2 g. of pyridine into a threeneck flask equipped with a thermometer and a stirrer, and the reaction was effected for hours under agitation in a mantle heater maintained at 80 C. At the end of the reaction, the reaction mixture was poured into water and insoluble matters were separated by filtration. The laking of the resulting dye was effected by addition of an aqueous solution of barium chloride and the precipitating red product was recovered by filtration, washed with water and dried.

The above reaction is expressed by the following formula:

(i) 01 NaOzS (I) C1 A 30 A 3 mHavNHa BaCl Y I I l 1 O S a 133.0 5 (II) NHCmHW 11,70, 11 S0 Ba/2 Preparation of liquid developer: A liquid developer was prepared by dispersing 0.2 g. of the so,formed lake into a mixed solvent of 200 ml. of xylene and 800 ml. of Isopar H (isoparaffin hydrocarbon, product of Esso Standard Petroleum Co.) by means of ultrasonic vibration. The resulting liquid developer was excellent in dispersibility of particles and the particles were absorbed onto a negative electrostatic latent image, forming a beautiful pink visible image (positive) of good fixing property.

EXAMPLE 25 Synthesis: An aqueous solution. of a violet dye prepared by coupling a diazotized product of octadecylaniline with H acid in an alkaline medium was heated at 50 C., and an aqueous solution of potassium chloride was added thereto under agitation. The mixture was stirred for 1 hour at 50 C., following which the resulting precipitate was recovered by filtration, washed with water and dried to yield a red product of the following formula:

HO NH:

08/2035 SOJCB/Z Preparation of liquid developer: A liquid developer was prepared by dispersing 0.2 g. of the so formed red product into a mixed solvent of 150 ml. of Solvesso (aromatic hydrocarbon solvent, product of Esso Standard Petroleum Co.) and 850 ml. of Shellsol 72 (isoparafiin hydrocarbon, product of Shell Petroleum Co.) by operating a homogenizing mixer for 10 minutes. The par-. ticles dispersed in the so formed liquid developer were absorbed onto a negative electrostatic latent image, forming a distinct red visible image (positive).

What we claim is:

l. A liquid developer for electrophotography which consists essentially of a dispersion of an uncoated acidic azo dye or pigment in an electrically insulating hydrocarbon liquid, said azo dye or pigment having the formula wherein A and A each represent a benzene, naphthalene or pyrazolone ring which may be substituted by a halogen atom; a hydroxyl group; an amino group; a nitro group; $0 M wherein M is hydrogen, an alkali metal or an alkaline earth metal; an alkyl or alkoxy group having 1 to 4 carbon atoms; or a phenyl group which may be substituted by a nitrogen atom, a hydroxyl group, an amino group, a nitro group of .SO M wherein M is as definedabove; R and R each represent an alkyl group of 8 to 24 carbon atoms; n is 0 or 1; and Y is an arylene group which may be substituted by an alkyl or alkoxy group of l to v4 carbon atoms; the liquid developer con taining 0.05'to 5 grams of said dye or pigment per liter of said liquid developer. I

2. The liquid developer of claim 1 wherein said liquid hydrocarbon is a liquid aliphatic hydrocarbon containing 5 to 30% by volume of an aromatic hydrocarbon.

21 22 3. The liquid developer of claim 1, wherein said azo dye is NHg NH:

12 CizH25 OaNa SOaNa 4. The liquid developer of claim 1, wherein said azo dye is OH GHQO OCH; (HI

1aHa1 CIBHIH oaNa S03 5. The liquid developer of claim 1, wherein said azo dye is OH SOQNB CHQO OCHa 022B SQONB.

6. The liquid developer of claim 1, wherein said azo 9. The liquid developer of claim 1, wherein said azo dye is: dye is NH: OH

H? CN SO Na 1 Hols son; 0

AH, 10. The liquid developer of claim 1, wherein said azo dye is 7. The liquid developer of claim 1, wherein said azo OH dye is CraHgi-N=N 0H NHCOCH; (Ia/20 s v S0 Ca/2 References Cited Na0 S -S0 Na UNITED STATES PATENTS 3,244,633 4/1966 Yellin et a1. 252-621 3,384,632 5/1968 SOIOdaI 25262.1 2,121,017 6/1938 Cantrell 260-197 3,052,667 9/1962 Harford et al 260205 09,910 1968 t' 8. The liquid developer of claim 1, wherein said azo 3,376,484 Z1937 ggsg ffi dye 2,150,787 3/1939 Schultis et a1. 260-198 on NHCOCHS FOREIGN PATENTS 1,016,072 1/ 1966 Great Britain .6 252-621 NORMAN G. TORCHIN, Primary Examiner some/2 I. P. BRAMMER, Assistant Examiner v: v UNITED STAT PATENT OFFICE CERTIFlCATE OF CORRECTION Patent: No. 3,781,208 Dated December 25, 1973 Inventor(s) Yasuo Ueda, Kobe, Yasutoki Kamezawa and Tatsuo A";z wa It is certif' 1e% that error appears in the above-identified patent and that said Letters Patentv are hereby corrected as shown below:

Claim 4, delete the formula and insert the following: I -I j "0H CH30 0on 0H V t I c H N=N. N=N@3 .c 11

Claim 5, delete the formula and insert the following:

CH3O 0CH3' SO Na I N=N N=N S03Na v t Y NR3 0H I Signed and sealed this 17th day of September 1974.

(SEAL) Attest: I I

I c. MARSHALL DANN izi gt ng f ge I v Commissioner of Patents FORM era-1050 (10-6 9) USCOMWDC mwhpsg 

